The present invention relates to certain novel naphthopyran compounds. More particularly, this invention relates to photochromic naphthopyrans having substituents that make the compounds more compatible for use in different matrices, e.g., hydrophilic or hydrophobic polymeric matrices. This invention also relates to compositions and articles containing such novel photochromic compounds. When exposed to electromagnetic radiation containing ultraviolet rays, such as the ultraviolet radiation in sunlight or the light of a mercury lamp, many photochromic compounds exhibit a reversible change in color. When the ultraviolet radiation is discontinued, such a photochromic compound will return to its original color or colorless state.
Various classes of photochromic compounds have been synthesized and suggested for use in applications in which a sunlight-induced reversible color change or darkening is desired. U.S. Pat. No. 3,567,605 (Becker) describes a series of pyran derivatives, including certain benzopyrans and naphthopyrans. U.S. Pat. No. 5,458,814 describes photochromic 2,2-di-substituted-5,6-substituted-2H-naphtho[1,2-b]pyran compounds primarily for use in lenses and other plastic transparencies. These compounds have an acceptable fade rate in addition to a high activated intensity and a high coloration rate. U.S. Pat. No. 5,585,042 discloses 3,3-di-substituted-8-substituted-3H-naphtho[2,1-b]pyran compounds for similar uses. These compounds exhibit an improved solar response, a higher activating wavelength than unsubstituted naphthopyrans, and an acceptable bleach or fade rate. U.S. Pat. No. 5,645,767 describes photochromic indeno[2,1-f]naphtho[1,2-b]pyrans having a high activated intensity, an acceptable fade rate and high coloration rate.
International Patent Application WO 97/05213 describes a photochromic monomer having a photochromic dye moiety bonded to an organic spacer group which terminates with a polymerizable group. It is reported that when the photochromic monomer is incorporated into a cross-linking polymerizable casting composition, the photochromic material has a reduced sensitivity to temperature.
Although 3H-naphtho[2,1-b]pyrans, 2H-naphtho[1,2-b]pyrans and indeno[2,1-f]naphtho[1,2-b]pyrans of good intensity and reasonable fade are currently available, in certain circumstances it is desirable to modify the comparability of the photochromic compound with the substrate or host material. By making the photochromic compound more compatible with the polymeric matrix, it is less likely that the combination will demonstrate cloudiness or haze and phase separation which may become evident as the formation of crystals within the matrix or a bloom on the surface resulting from the migration of the photochromic after curing, and it is more likely that the photochromic compound will be more soluble and uniformly distributed throughout the matrix. Other properties of the photochromic compounds that may or may not be effected by the substituents of the present invention include fade and/or activation rate, saturated optical density, molar absorptivity or molar extinction coefficient, activated color and leachability from the polymeric matrix. Modifications to such properties may be done to match the same properties of complementary photochromic compounds or to enable the use of such compounds in hydrophilic or hydrophobic coatings, thin films or in rigid to flexible plastic matrices, e.g., contact lenses.
In accordance with the present invention, there have been discovered novel photochromic compounds; namely, certain 2H-naphtho[1,2-b]pyrans, 3H-naphtho[2,1-b]pyrans and indeno[2,1-f]naphtho[1,2-b]pyrans, that have at least one substituent containing terminal and/or pendant groups selected from hydroxyl, carboxyl, sulfo, sulfono, (meth)acryloxy, 2-(methacryloxy)ethylcarbamyl (xe2x80x94OC(O)NHC2H4OC(O)C(CH3)xe2x95x90CH2), epoxy or a mixture thereof. The substituent having the aforementioned groups is a residue of an alkoxylated diol or an organic polyol. Appropriate selection of the substituent, e.g., chain length, the number and type of the terminal and/or pendant groups, enables modification of the aforementioned properties. For example, an increase in the number of or altering the type of substituents on the naphthopyran having terminal groups selected from hydroxyl, carboxyl, sulfo, sulfono or a mixture thereof causes an improvement in the substituted compounds compatibility with polar or hydrophilic matrices and vice versa. Use of the polymerizable groups, epoxy, (meth)acryloxy, i.e., acryloxy or methacryloxy, or 2-(methacryloxy)ethylcarbamyl with or without the aforementioned groups on the substituent enables reacting and binding the photochromic compound into the polymeric matrix to prevent extraction or leaching of the photochromics for example, when the matrix is in contact with liquids. Depending on the location of the previously mentioned substituent(s), certain other substituents may also be present on the naphtho, pyrano and indeno portions of the aforedescribed compounds.
In accordance with the present invention, it has been discovered that certain properties, e.g., solubility and/or compatability in hydrophilic coatings, films and plastics, leachability, fade rate, activation rate, saturated optical density, fatigue rate, and molar absorption of selected photochromic 2H-naphtho[1,2-b]pyrans, 3H-naphtho[2,1-b]pyrans and indeno[2,1-f]naphtho[1,2-b]pyrans may be modified by including on such compounds at least one substituent containing terminal and/or pendant groups selected from hydroxyl, carboxyl, sulfo, sulfono, (meth)acryloxy, 2-(methacryloxy)ethylcarbamyl, epoxy or a mixture thereof. The substituent may be located on the naphtho, indeno and/or on the pyrano portion of the naphthopyran.
Other than where otherwise indicated, all numbers expressing values, such as, wavelengths, quantities of ingredients or reaction conditions used herein are to be understood as modified in all instances by the term xe2x80x9caboutxe2x80x9d which means near to in number, quantity, degree, etc.
The disclosures of the related applications, patents and articles cited herein describing materials and/or procedures for making materials such as extended triols, polyester polyols, polycarbonate polyols, carbohydrates, macrocyclic acetals containing lipophilic substituents, propargyl alcohols, photochromic compounds, polymeric host materials, contact lenses and coating application methods are incorporated herein, in toto, by reference.
The naphthopyrans of the present invention also may have certain other substituents. Specifically, the 2H-naphthopyrans may have substituents at the 5 and 6 positions and may have additional substituents at the 7, 8, 9 and 10 positions; the 3H-naphthopyrans may have substituents at the 8 and 9 positions and may have additional substituents at the 5 and 6 positions; and the indeno-fused naphthopyrans may have certain substituents at the 5, 6, 7, 8, 9, 10, 11, 12 or 13 positions. The aforedescribed naphthopyrans may be represented by graphic formulae I, II and III in which the internal numbers 1 through 13 identify the ring atoms of the naphthopyrans and letters a through n represent the sides of the naphthopyran rings. In the definition of the substituents shown in the following graphic formulae I, II and III, like symbols have the same meaning unless stated otherwise. 
In graphic formulae I, II and III, R1, R1xe2x80x2, R2, each R3, R4, R5 and R6 may be the group R. The R group may be represented by the following formulae IVA to IVF:
xe2x80x94Axe2x80x83xe2x80x83(IVA);
xe2x80x94Dxe2x80x94Axe2x80x83xe2x80x83(IVB);
xe2x80x94Dxe2x80x94Exe2x80x94Uxe2x80x83xe2x80x83(IVC);
xe2x80x94Dxe2x80x94Uxe2x80x83xe2x80x83(IVD);
xe2x80x94Exe2x80x94Uxe2x80x83xe2x80x83(IVE);
or
xe2x80x94Uxe2x80x83xe2x80x83(IVF);
wherein xe2x80x94A is represented by the following formula:
xe2x80x94[(OC2H4)x(OC3H6)y(OC4H8)z]xe2x80x94J
wherein xe2x80x94J is selected from: xe2x80x94OCH2COOH; xe2x80x94OCH(CH3)COOH; xe2x80x94OC(O)(CH2)wCOOH; xe2x80x94OC6H4SO3H; xe2x80x94OC5H10SO3H; xe2x80x94OC4H8SO3H; xe2x80x94OC3H6SO3H; xe2x80x94OC2H4SO3H; or xe2x80x94OSO3H; and w is an integer from 1 to 18, preferably from 2 to 12; wherein x, y and z are each a number between 0 and 50, and the sum of x, y and z is between 1 and 50; xe2x80x94Dxe2x80x94 is xe2x80x94C(O)xe2x80x94 or xe2x80x94CH2xe2x80x94; xe2x80x94Exe2x80x94 is represented by the following formula:
xe2x80x94[(OC2H4)x(OC3H6)y(OC4H8)z]xe2x80x94
wherein x, y and z are the same as defined for xe2x80x94A; xe2x80x94U is a residue of an organic polyol having at least 1 hydroxyl group or a derivative of the residue wherein one or more of the hydroxyl groups have been reacted to form the carboxyl, sulfo or sulfono group containing substituent xe2x80x94J, a polymerizable group selected from (meth)acryloxy, 2-(methacryloxy)ethylcarbamyl, or epoxy or a mixture thereof provided that xe2x80x94U is not the same as xe2x80x94Exe2x80x94OH.
The group, xe2x80x94U, is a residue of an organic polyol which is defined herein to include hydroxylated carbohydrates discussed hereinafter. The residue is formed by the reaction of one of the hydroxyl groups on the polyol with a precursor of group xe2x80x94Dxe2x80x94, such as a carboxylic acid or a methylene halide, a precursor of group xe2x80x94Exe2x80x94, such as polyalkylene glycol or a hydroxyl group as substituent R1, R1xe2x80x2, R2, each R3, R4, R5 or R6 on the naphthopyran of graphic formulae I, II or III. The organic polyol may be represented by G(OH)a and the residue xe2x80x94U may be represented by the formula xe2x80x94Oxe2x80x94G(OH)axe2x88x921, wherein G is the backbone or main chain of the polyhydroxylated compound and a is at least 2, provided that xe2x80x94U is not the same as xe2x80x94Exe2x80x94OH.
All, none or at least one of the hydroxyls of group, xe2x80x94U, may be reacted to form a group represented by xe2x80x94J, a polymerizable group selected from (meth)acryloxy, 2-(methacryloxy)ethylcarbamyl, epoxy or a mixture thereof. The hydroxyl groups of xe2x80x94U may be reacted to form the carboxyl group containing substituent xe2x80x94J by the method of Reactions B and D to produce a carboxylated organic polyol residue. The organic polyol residue xe2x80x94U having the sulfo or sulfono terminating groups of xe2x80x94J on it may be produced by acidic condensation of the hydroxyl groups of xe2x80x94U with HOC6H4SO3H; HOC5H10SO3H; HOC4H8SO3H; HOC3H6SO3H; HOC2H4SO3H; or H2SO4, respectively. The polymerizable groups, (meth)acryloxy, 2-(methacryloxy)ethylcarbamyl or epoxy, may be added to the polyol residue xe2x80x94U by condensation of the polyol with (meth)acryloyl chloride, isocyanatoethyl methacrylate or epichlorohydrin, respectively.
Examples of organic polyols that may be used as xe2x80x94U in the R group substituent of the polymer matrix compatibilized naphthopyrans of the present invention include polyols having at least 2 hydroxy groups such as (a) low molecular weight polyols, i.e., polyols having an average molecular weight less than 500, e.g., aliphatic triols, such as C2-C10 aliphatic triols, polyhydric alcohols and alkoxylated low molecular weight polyols; (b) polyester polyols; (c) polyether polyols; (d) amide-containing polyols; (e) epoxy polyols; (f) polyhydric polyvinyl alcohols; (g) urethane polyols; (h) polyacrylic polyols; (i) polycarbonate polyols; and (j) mixtures of such polyols.
Examples of low molecular weight polyols that can be used in the preparation of the photochromic compounds of the present invention include: tetramethylolmethane, i.e., pentaerythritol, dipentaerythritol, tripentaerythritol; trimethylolethane; trimethylolpropane; ditrimethylolpropane; 1,2,3-propanetriol, i.e., glycerol; 1,2-butanediol; di-(trimethylolpropane)dimethylol propionic acid; 2-(hydroxymethyl)-2-methyl-1,3-propanediol; 2-(hydroxymethyl)-2-ethyl-1,3-propanediol; and extended polyols. Extended polyols are reaction products having terminal hydroxyl groups of the polyol and a suitable reactant, e.g., an alkylene oxide, or a lactone. Examples of such extended polyols include xcex5-caprolactone extended trimethylol methane and ethoxylated or propoxylated trimethylolpropane or pentaerythitol having a number average molecular weight less than 500. Extended polyols having a number average molecular weight of 500 or more are described hereinafter as polyester polyols and polyalkoxylated polyols. Further examples of extended triols are disclosed in U.S. Pat. No. 4,398,008.
Polyester polyols are generally known and can have a number average molecular weight in the range of from 500 to 10,000. They are prepared by conventional techniques utilizing low molecular weight triols and polyhydric alcohols known in the art, including but not limited to the previously described low molecular weight polyols with polycarboxylic acids. Examples of suitable polycarboxylic acids include: phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, tetrahydrophthalic acid, adipic acid, succinic acid, glutaric acid, fumaric acid, and mixtures thereof. Anhydrides of the above acids, where they exist, can also be employed and are encompassed by the term xe2x80x9cpolycarboxylic acidxe2x80x9d. In addition, certain materials that react in a manner similar to acids to form polyester polyols are also useful. Such materials include lactones, e.g., caprolactone, propiolactone and butyrolactone, and hydroxy acids such as hydroxycaproic acid and dimethylol propionic acid. If a triol or polyhydric alcohol is used, a monocarboxylic acid, such as acetic acid and/or benzoic acid, may be used in the preparation of the polyester polyols, and for some purposes, such a polyester polyol may be desirable. Moreover, polyester polyols are understood herein to include polyester polyols modified with fatty acids or glyceride oils of fatty acids and/or alkylene oxides, e.g., ethylene oxide, propylene oxide, etc., to produce polyoxyethylene fatty acid esters such as polyoxyethylene (20) sorbitan monolaurate and related polysorbates. Further examples of polyester polyols having ether and ester groups are described in U.S. Pat. No. 4,677,181.
Polyether polyols are generally known and can have a number average molecular weight in the range of from 500 to 10,000. Examples of polyether polyols include various polyoxyalkylene polyols and polyalkoxylated polyols each having at least 2 hydroxyl groups and a number average molecular weight greater than 500. The polyether polyols can be prepared, according to well-known methods, by condensing alkylene oxide, or a mixture of alkylene oxides using acid or base catalyzed addition, with a polyhydric initiator or a mixture of polyhydric initiators such as low molecular weight polyols, sorbitol and the like. Illustrative alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, amylene oxide, aralkylene oxides, e.g., styrene oxide, and the halogenated alkylene oxides such as trichlorobutylene oxide and so forth. The more preferred alkylene oxides include propylene oxide and ethylene oxide or a mixture thereof using random or step-wise oxyalkylation.
Amide-containing polyols are generally known and typically are prepared from the reaction of diacids or lactones and low molecular weight polyols described herein with diamines or aminoalcohols as described hereinafter. For example, amide-containing polyols may be prepared by the reaction of neopentyl glycol, adipic acid and hexamethylenediamine. The amide-containing polyols may also be prepared through aminolysis by the reaction, for example, of carboxylates, carboxylic acids, or lactones with amino alcohols. Examples of suitable diamines and amino alcohols include hexamethylenediamines, ethylenediamines, phenylenediamine, monoethanolamine, diethanolamine, isophorone diamine and the like.
Epoxy polyols are generally known and can be prepared, for example, by the reaction of glycidyl ethers of polyphenols such as the diglycidyl ether of 2,2-bis(4-hydroxyphenyl)propane, with polyphenols such as 2,2-bis(4-hydroxyphenyl)propane. Epoxy polyols of varying molecular weights and average hydroxyl functionality can be prepared depending upon the ratio of starting materials used.
Polyhydric polyvinyl alcohols are generally known and can be prepared, for example, by the polymerization of vinyl acetate in the presence of suitable initiators followed by hydrolysis of at least a portion of the acetate moieties. In the hydrolysis process, hydroxyl groups are formed which are attached directly to the polymer backbone. In addition to homopolymers, copolymers of vinyl acetate and monomers such as vinyl chloride can be prepared and hydrolyzed in similar fashion to form polyhydric polyvinyl alcohol-polyvinyl chloride copolymers.
Urethane polyols are generally known and can be prepared, for example, by reaction of a polyisocyanate with excess organic polyol to form a hydroxyl functional product having at least 2 hydroxyl groups. Examples of polyisocyanates useful in the preparation of urethane polyols include those selected from the group consisting of aliphatic, aromatic, cycloaliphatic and heterocyclic polyisocyanates, and mixtures of such polyisocyanates.
Specific examples of polyisocyanates useful in the preparation of urethane polyols include, but are not limited to, toluene-2,4-diisocyanate; toluene-2,6-diisocyanate; diphenyl methane-4,4xe2x80x2-diisocyanate; diphenyl methane-2,4xe2x80x2-diisocyanate; para-phenylene diisocyanate; biphenyl diisocyanate; 3,3xe2x80x2-dimethyl-4,4xe2x80x2-diphenylene diisocyanate; tetramethylene-1,4-diisocyanate; hexamethylene-1,6-diisocyanate; 2,2,4-trimethyl hexane-1,6-diisocyanate; lysine methyl ester diisocyanate; bis(isocyanato ethyl)fumarate; isophorone diisocyanate; ethylene diisocyanate; dodecane-1,12-diisocyanate; cyclobutane-1,3-diisocyanate; cyclohexane-1,3-diisocyanate; cyclohexane-1,4-diisocyanate; methyl cyclohexyl diisocyanate; hexahydrotoluene-2,4-diisocyanate; hexahydrotoluene-2,6-diisocyanate; hexahydrophenylene-1,3-diisocyanate; hexahydrophenylene-1,4-diisocyanate; perhydrodiphenylmethane-2,4xe2x80x2-diisocyanate; perhydrodiphenylmethane-4,4xe2x80x2-diisocyanate and mixtures thereof.
Examples of organic polyols useful in the preparation of urethane polyols include the other polyols described herein, e.g., low molecular weight polyols, polyester polyols, polyether polyols, amide-containing polyols, epoxy polyols, polyhydric polyvinyl alcohols, polyacrylic polyols, polycarbonate polyols and mixtures thereof.
The polyacrylic polyols are generally known and can be prepared by free-radical addition polymerization techniques of monomers described hereinafter. Preferably the polyacrylic polyols have a weight average molecular weight of from 500 to 20,000 and a hydroxyl number of from 20 to 225.
Polyacrylic polyols include, but are not limited to, the known hydroxyl-functional addition polymers and copolymers of acrylic and methacrylic acids; their ester derivatives including, but not limited to, their hydroxyl-functional ester derivatives. Examples of hydroxy-functional ethylenically unsaturated monomers to be used in the preparation of the hydroxy-functional addition polymers include hydroxyethyl(meth)acrylate, i.e., hydroxyethyl acrylate and hydroxyethyl methacrylate, hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate, hydroxymethylethyl acrylate, hydroxymethylpropyl acrylate and mixtures thereof.
More preferably, the polyacrylic polyol is a copolymer of hydroxy-functional ethylenically unsaturated (meth)acrylic monomers and other ethylenically unsaturated monomers selected from the group consisting of vinyl aromatic monomers, e.g., styrene, xcex1-methyl styrene, t-butyl styrene and vinyl toluene; vinyl aliphatic monomers such as ethylene, propylene and 1,3-butadiene; (meth)acrylamide; (meth)acrylonitrile; vinyl and vinylidene halides, e.g., vinyl chloride and vinylidene chloride; vinyl esters, e.g., vinyl acetate; alkyl esters of acrylic and methacrylic acids, i.e. alkyl esters of (meth)acrylic acids, having from 1 to 17 carbon atoms in the alkyl group, including methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, cyclohexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, isobornyl(meth)acrylate and lauryl(meth)acrylate; epoxy-functional ethylenically unsaturated monomers such as glycidyl(meth)acrylate; carboxy-functional ethylenically unsaturated monomers such as acrylic and methacrylic acids and mixtures of such ethylenically unsaturated monomers.
The hydroxy-functional ethylenically unsaturated (meth)acrylic monomer(s) may comprise up to 95 weight percent of the polyacrylic polyol copolymer. Preferably it composes up to 70 weight percent, and more preferably, the hydroxy-functional ethylenically unsaturated (meth)acrylic monomer(s) comprises up to 45 weight percent of the total copolymer.
The polyacrylic polyols described herein can be prepared by free radical initiated addition polymerization of the monomer(s), and by organic solution polymerization techniques. The monomers are typically dissolved in an organic solvent or mixture of solvents including ketones such as methyl ethyl ketones, esters such as butyl acetate, the acetate of propylene glycol, and hexyl acetate, alcohols such as ethanol and butanol, ethers such as propylene glycol monopropyl ether and ethyl-3-ethoxypropionate, and aromatic solvents such as xylene and SOLVESSO 100, a mixture of high boiling hydrocarbon solvents available from Exxon Chemical Co. The solvent is first heated to reflux, usually 70 to 160xc2x0 C., and the monomer or a mixture of monomers and free radical initiator is slowly added to the refluxing solvent, over a period of about 1 to 7 hours. Adding the monomers too quickly may cause poor conversion or a high and rapid exothermic reaction, which is a safety hazard. Suitable free radical initiators include t-amyl peroxyacetate, di-t-amyl peroxyacetate and 2,2xe2x80x2-azobis(2-methylbutanenitrile). The free radical initiator is typically present in the reaction mixture at from 1 to 10 percent, based on total weight of the monomers. The polymer prepared by the procedures described herein is non-gelled and preferably has a weight average molecular weight of from 500 to 20,000 grams per mole.
Polycarbonate polyols that can be used to prepare the photochromic compounds of the present invention may be obtained by reacting polyhydric alcohols with a carbonyl component selected from phosgene, a chloroformate, a dialyl carbonate, a diaryl carbonate, an alkylene carbonate or a mixture thereof. Such polycarbonate polyol production methods are described in U.S. Pat. Nos. 3,689,609, 3,689,462, 4,131,731; 4,160,853; 4,533,729, 4,891,421 and 5,266,551.
Polycarbonate polyols having 2 or more hydroxyl groups may also be prepared by the ester interchange reaction of a polycarbonate diol with a triol and/or a tetraol, as described in U.S. Pat. No. 5,143,997. Introduction of carboxyl groups into the polycarbonate polyols may be accomplished by the reaction of a polycarbonate polyol with an acid anhydride or a dicarboxylic acid, as described in U.S. Pat. No. 5,527,879.
Examples of polyhydroxylated carbohydrates that can be used in the R group substituent of the photochromic compounds of the present invention include: low molecular weight carbohydrates of the formula Cn(H2O)n wherein n is from 3 to 5, e.g., aldotriose, aldoketose, erythrose, ribose, etc.; monosaccharides, e.g., simple sugars such as glucose and fructose; oligosaccharides, i.e., carbohydrates containing from two to ten monosaccharides linked together, e.g., sucrose and cyclodextrins; polysaccharides, i.e., carbohydrates containing more than ten monosaccharides linked together by glycosidic bonds, e.g., starch, cellulose, glycogen, pectin, agar, carrageenan and natural gums such as arabic and tragacanth.
The polyhydroxylated carbohydrates described herein also include glycosides which are mono- and oligosaccharides linked to nonsugar organic compounds. An example of which is the product of the reaction of D-glucose with ethanol to form ethyl xcex1- and xcex2-D-glucopyranosides. Another class of polyhydroxylated carbohydrates are the glycoconjugates composed of glycoproteins, proteoglycans, peptidoglycans and glycolipids. Still another class of carbohydrates includes various reaction products such as the sugar alcohols, e.g., xylitol and glucitol, produced by the reduction of mono- and oligosaccharides. A further group of reaction products include low molecular weight carbohydrates, mono- and oligosaccharides in which one or more of the hydroxyl groups has been oxidized to a carboxylic acid functional group, or replaced by an amino group, thiol group or a halogen atom. Further information about carbohydrates that may be suitable for use in the R-group is found in the Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, 1992, Volume 4, pages 911-948.
Preferably, the xe2x80x94U group is selected from low molecular weight polyols and extended polyols. Examples of such polyols include (a) glycerol, pentaerythritol and trimethylolpropane, (b) ethoxylated glycerol, ethoxylated pentaerythritol and ethoxylated trimethyolpropane; and (c) polyols (a) and (b) having at least 1 hydroxyl group reacted to produce substituent xe2x80x94J, a polymerizable group selected from (meth)acryloxy, 2-(methacryloxy)ethylcarbamyl or epoxy, or a mixture thereof.
The group, xe2x80x94(OC2H4)xxe2x80x94, represents poly(ethylene oxide); xe2x80x94(OC3H6)yxe2x80x94, represents poly(propylene oxide); and, xe2x80x94(OC4H8)zxe2x80x94, represents poly(butylene oxide). When used in combination, the poly(ethylene oxide), poly(propylene oxide) and poly(butylene oxide) groups of R may be in a random or block order within the R moiety. The letters x, y and z are each a number between 0 and 50 and the sum of x, y and z is between 1 and 50. The sum of x, y and z may be any number that falls within the range of 1 to 50, e.g., 1, 2, 3 . . . 50. The sum may also range from any lower number to any higher number within the range of 1 to 50, e.g., 6 to 50, 31 to 50. The numbers for x, y, and z are average values and can be partial numbers, e.g., 9.5.
Alternatively, R1 is hydrogen, C1-C3 alkyl or the group, xe2x80x94C(O)W, W being xe2x80x94OR7, xe2x80x94N(R8)R9, piperidino or morpholino, wherein R7 is allyl, C1-C6 alkyl, phenyl, mono(C1-C6)alkyl substituted phenyl, mono(C1-C6)alkoxy substituted phenyl, phenyl(C1-C3)alkyl, mono(C1-C6)alkyl substituted phenyl(Cl-C3)alkyl, mono(C1-C6)alkoxy substituted phenyl(C1-C3)alkyl, C1-C6 alkoxy(C2-C4)alkyl or C1-C6 haloalkyl; R8 and R9 are each selected from the group consisting of C1-C6 alkyl, C5-C7 cycloalkyl, phenyl and mono- or di-substituted phenyl, said phenyl substituents being selected from C1-C6 alkyl and C1-C6 alkoxy, and said halo substituent being chloro or fluoro. R1xe2x80x2 is the same as R1 except that R1xe2x80x2 is not hydrogen.
R2 may be selected from the group consisting of the group R, mono-R-substituted phenyl, hydrogen, C1-C6 alkyl, C3-C7 cycloalkyl, phenyl, mono- or di-substituted phenyl and the groups xe2x80x94OR10 and xe2x80x94OC(O)R10, wherein R10 is C1-C6 alkyl, phenyl(C1-C3)alkyl, mono(C1-C6)alkyl substituted phenyl(C1-C3)alkyl, mono(C1-C6)alkoxy substituted phenyl(C1-C3)alkyl, C1-C6 alkoxy(C2-C4)alkyl, C3-C7 cycloalkyl or mono(C1-C4)alkyl substituted C3-C7 cycloalkyl, n is selected from the integers 0, 1 and 2 and said phenyl substituents are the same as for R1.
Each R3 and R4 may be selected from the group consisting of the group R, hydrogen, C1-C6 alkyl, C3-C7 cycloalkyl, phenyl, mono- or di-substituted phenyl and the groups xe2x80x94OR10 and xe2x80x94OC(O)R10, wherein R10 is C1-C6 alkyl, phenyl(C1-C3)alkyl, mono(C1-C6)alkyl substituted phenyl(C1-C3)alkyl, mono(C1-C6)alkoxy substituted phenyl(C1-C3)alkyl, C1-C6 alkoxy(C2-C4)alkyl, C3-C7 cycloalkyl or mono(C1-C4)alkyl substituted C3-C7 cycloalkyl, n is selected from the integers 0, 1 and 2 and said phenyl substituents are the same as for R1.
R5 and R6 may together form an oxo group, a spiro-carbocyclic ring containing 3 to 6 carbon atoms or a spiro-heterocyclic group containing 1 or 2 oxygen atoms and 3 to 6 carbon atoms including the spirocarbon atom and both rings may be benz-annelated with one or two benzene groups. Examples of the spiro-carbocyclic ring substituents include spirofluoreno, spirocyclopropyl, spirocyclobutyl, spirocyclopentyl, spirocyclohexyl, spiroindan-1-yl, spiroindan-2-yl, etc. Examples of the spiro-heterocyclic group include spiroxantheno and compounds which may be represented by the expression (xe2x80x94Oxe2x80x94(C2-C5 alkanediyl)-Oxe2x80x94), e.g., spiro-1,3-dioxolane-2, spiro-1,3-dioxane-2, etc., or spirolactones, such as butyrolactone, propiolactone, etc. Alternatively, R5 and R6 may each be the group R, hydrogen, hydroxy, C1-C6 alkyl, C3-C7 cycloalkyl, allyl, phenyl, mono-substituted phenyl, benzyl, mono-substituted benzyl, chloro, fluoro, the group xe2x80x94C(O)X, wherein X is hydroxy, C1-C6 alkyl, C1-C6 alkoxy, phenyl, mono-substituted phenyl, amino, mono(C1-C6)alkylamino, or di(C1-C6)alkylamino, e.g., dimethyl amino, methyl propyl amino, etc., or R5 and R6 may each be the group, xe2x80x94OR11, wherein R11 is C1-C6 alkyl, phenyl(C1-C3)alkyl, mono(C1-C6)alkyl substituted phenyl(C1-C3)alkyl, mono(C1-C6)alkoxy substituted phenyl(C1-C3)alkyl, C1-C6 alkoxy(C2-C4)alkyl, C3-C7 cycloalkyl, mono(C1-C4)alkyl substituted C3-C7 cycloalkyl, C1-C6 chloroalkyl, C1-C6 fluoroalkyl, allyl, the group, xe2x80x94CH(R12)Y, wherein R12 is hydrogen or C1-C3 alkyl and Y is CN, CF3, or COOR13, and R13 is hydrogen or C1-C3 alkyl, or R11 is the group, xe2x80x94C(O)Z, wherein Z is hydrogen, C1-C6 alkyl, C1-C6 alkoxy, the unsubstituted, mono- or di-substituted aryl groups, phenyl or naphthyl, phenoxy, mono- or di-(C1-C6)alkyl substituted phenoxy, mono- or di-(C1-C6)alkoxy substituted phenoxy, mono- or di-(C1-C6)alkoxy substituted phenoxy, amino, mono(C1-C6)alkylamino, di(C1-C6)alkylamino, phenylamino, mono- or di(C1-C6)alkyl substituted phenylamino, or mono- or di-(C1-C6)alkoxy substituted phenylamino, each of the aforedescribed phenyl, benzyl and aryl group substituents being C1-C6 alkyl or C1-C6 alkoxy.
B and Bxe2x80x2 are each selected from the group consisting of: (a) mono-R-substituted phenyl; (b) the unsubstituted, mono-, di- and tri-substituted aryl groups, phenyl and naphthyl; (c) 9-julolidinyl and the unsubstituted, mono- and di-substituted heteroaromatic groups pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, carbazolyl and fluorenyl, each of said aryl and heteroaromatic substituents in (b) and (c) being selected from the group consisting of hydroxy, aryl, mono(C1-C6)alkoxyaryl, di(C1-C6)alkoxyaryl, mono(C1-C6)alkylaryl, di(C1-C6)alkylaryl, chloroaryl, fluoroaryl, C3-C7 cycloalkylaryl, C3-C7 cycloalkyl, C3-C7 cycloalkyloxy, C3-C7 cycloalkyloxy(C1-C6)alkyl, C3-C7 cycloalkyloxy(C1-C6)alkoxy, aryl(C1-C6)alkyl, aryl(C1-C6)alkoxy, aryloxy, aryloxy(C1-C6)alkyl, aryloxy(C1-C6)alkoxy, mono- and di-(C1-C6)alkylaryl(C1-C6)alkyl, mono- and di-(C1-C6)alkoxyaryl(C1-C6)alkyl, mono- and di-(C1-C6)alkylaryl(C1-C6)alkoxy, mono- and di-(C1-C6)alkoxyaryl(C1-C6)alkoxy, amino, mono(C1-C6)alkylamino, di(C1-C6)alkylamino, diarylamino, N-(C1-C6)alkylpiperazino, N-arylpiperazino, aziridino, indolino, piperidino, arylpiperidino, morpholino, thiomorpholino, tetrahydroquinolino, tetrahydroisoquinolino, pyrryl, C1-C6 alkyl, C1-C6 chloroalkyl, C1-C6 fluoroalkyl, C1-C6 alkoxy, mono(C1-C6)alkoxy(C1-C4)alkyl, acryloxy, methacryloxy, bromo, chloro and fluoro, each aryl group described for said aryl or heteroaromatic substituent being phenyl or naphthyl; (d) the unsubstituted or mono-substituted groups, pyrazolyl, imidazolyl, pyridyl, pyrazolinyl, imidazolinyl, pyrrolinyl, phenothiazinyl, phenoxazinyl, phenazinyl or acridinyl, each of said substituents for said groups in (d) being selected from the group consisting of C1-C6 alkyl, C1-C6 alkoxy, phenyl, fluoro, chloro and bromo; (e) monosubstituted phenyl, having a substituent at the para position that is the linking group, xe2x80x94(CH2)txe2x80x94 or xe2x80x94Oxe2x80x94(CH2)txe2x80x94, wherein t is the integer 1, 2, 3, 4, 5 or 6, connected to an aryl group, e.g. phenyl or naphthyl, which is a member of another photochromic naphthopyran, such as naphtho[2,1-b]pyran or naphtho[1,2-b]pyran; (f) the groups represented by the following graphic formulae VA and VB: 
wherein L is carbon or oxygen and M is oxygen or substituted nitrogen, provided that when M is substituted nitrogen, L is carbon, said nitrogen substituents being selected from the group consisting of hydrogen, C1-C6 alkyl and C2-C6 acyl; each R14 is C1-C6 alkyl, C1-C6 alkoxy, hydroxy, chloro or fluoro; R15 and R16 are each hydrogen or C1-C6 alkyl; and q is the integer 0, 1 or 2; (g) C1-C6 alkyl, C1-C6 chloroalkyl, C1-C6 fluoroalkyl, C1-C6 alkoxy(C1-C4)alkyl, C3-C6 cycloalkyl, mono(C1-C6)alkoxy(C3-C6)cycloalkyl, mono(C1-C6)alkyl(C3-C6)-cycloalkyl, chloro(C3-C6)cycloalkyl, fluoro(C3-C6)cycloalkyl and C4-C12 bicycloalkyl; and (h) the group represented by the following graphic formula VC: 
wherein P is hydrogen or C1-C4 alkyl and Q is selected from the unsubstituted, mono-, and di-substituted members of the group consisting of naphthyl, phenyl, furanyl and thienyl, each of said group substituents in (h) being C1-C4 alkyl, C1-C4 alkoxy, fluoro or chloro.
Alternatively, B and Bxe2x80x2 taken together may form fluoren-9-ylidene, mono-, or di-substituted fluoren-9-ylidene or form a member selected from the group consisting of saturated C3-C12 spiro-monocyclic hydrocarbon rings, e.g., cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclooctylidene, cyclononylidene, cyclodecylidene cycloundecylidene, and cyclododecylidene, saturated C7-C12 spiro-bicyclic hydrocarbon rings, e.g., bicyclo[2.2.1]heptylidene, i.e., norbornylidene, 1,7,7-trimethyl bicyclo[2.2.1]heptylidene, i.e., bornylidene, bicyclo[3.2.1]octylidene, bicyclo[3.3.1]nonan-9-ylidene, bicyclo[4.3.2]undecane, and saturated C7-C12 spiro-tricyclic hydrocarbon rings, e.g., tricyclo[2.2.1.02,6]heptylidene, tricyclo[3.3.1.13,7]decylidene, i.e., adamantylidene, and tricyclo[5.3.1.12,6]dodecylidene, each of said fluoren-9-ylidene substituents being selected from the group consisting of C1-C4 alkyl, C1-C4 alkoxy, fluoro and chloro, provided that there is at least one R group or mono-R-substituted phenyl on the naphthopyran. For example, the number of R groups (including the mono-R-substituted phenyl) may be 2, 3, 4, 5 or a number equal to the total number of substituents possible on the naphthopyran. When there is more than one R group or mono-R-substituted phenyl on the naphthopyran, the R groups may be the same or different, e.g., there may be two different groups selected from formulae IVA to IVF. Also, the naphthopyran of the present invention may have only one R-group or mono-R-substituted phenyl.
Preferably, the naphthopyran of the present invention is represented by graphic formula I or III, the R group is represented by formulae: IVA, IVB, IVE or IVF; R1xe2x80x2 is the group R, or R1xe2x80x2 is the group, xe2x80x94C(O)W, W being xe2x80x94OR7 or xe2x80x94N(R8)R9, wherein R7 is C1-C4 alkyl, phenyl, mono(C2-C4)alkyl substituted phenyl, mono(C1-C4)alkoxy substituted phenyl, phenyl(C1-C2)alkyl, mono(C1-C4)alkyl substituted phenyl(C1-C2)alkyl, mono(C1-C4)alkoxy substituted phenyl(C1-C2)alkyl, mono(C1-C4)alkoxy(C2-C3)alkyl or C1-C4 haloalkyl; R8 and R9 are each selected from the group consisting of C1-C4 alkyl, C5-C7 cycloalkyl, phenyl and mono- or di-substituted phenyl, said phenyl substituents being C1-C4 alkyl or C1-C4 alkoxy, and said halo substituents being chloro or fluoro. More preferably, R1xe2x80x2 is the group R or the group, xe2x80x94C(O)W, wherein W is the group, xe2x80x94OR7, and R7 is a C1-C3 alkyl.
Preferably, R2 is selected from the group consisting of the group R, mono-R-substituted phenyl, hydrogen, C1-C3 alkyl, C3-C5 cycloalkyl, phenyl, mono- or di-substituted phenyl and the group xe2x80x94OR10, wherein R10 is C1-C4 alkyl, phenyl(C1-C2)alkyl, mono(C1-C4)alkyl substituted phenyl(C1-C2)alkyl, mono(C1-C4)alkoxy substituted phenyl(C1-C2)alkyl, C1-C4 alkoxy(C2-C4)alkyl, C5-C7 cycloalkyl or mono(C1-C3)alkyl substituted C5-C7 cycloalkyl, and the phenyl substituents are C1-C3 alkyl or C1-C3 alkoxy. More preferably, R2 is selected from the group consisting of hydrogen, the group R, mono-R-substituted phenyl, C1-C3 alkyl, phenyl, mono- or di-substituted phenyl and the group xe2x80x94OR10, wherein R10 is C1-C3 alkyl and said phenyl substituents are methyl or methoxy.
Preferably, each R3 is selected from the group consisting of the group R, hydrogen, C1-C3 alkyl, C3-C5 cycloalkyl, phenyl, mono- or di-substituted phenyl and the group xe2x80x94OR10, wherein R10 is C1-C4 alkyl, phenyl(C1-C2)alkyl, mono(C1-C4)alkyl substituted phenyl(C1-C2)alkyl, mono(C1-C4)alkoxy substituted phenyl(C1-C2)alkyl, C1-C4 alkoxy(C2-C4)alkyl, C5-C7 cycloalkyl or mono(C1-C3)alkyl substituted C5-C7 cycloalkyl, and the phenyl substituents are C1-C3 alkyl or C1-C3 alkoxy.
Preferably, R5 and R6 are each selected from the group consisting of the group R, hydrogen, hydroxy, C1-C4 alkyl, C3-C6 cycloalkyl, chloro, fluoro and the group, xe2x80x94OR11, wherein R11 is C1-C3 alkyl, phenyl(C1-C2)alkyl, mono(C1-C3)alkyl substituted phenyl(C1-C3)alkyl, mono(C1-C3)alkoxy substituted phenyl(C1-C3)alkyl, C1-C3 alkoxy(C2-C4)alkyl, C1-C3 chloroalkyl, C1-C3 fluoroalkyl, the group, xe2x80x94CH(R12)Y, wherein R12 is hydrogen or C1-C2 alkyl and Y is CN or COOR13, R13 being hydrogen or C1-C2 alkyl, or R11 is the group, xe2x80x94C(O)Z, wherein Z is hydrogen, C1-C3 alkyl, C1-C3 alkoxy, phenyl, naphthyl, the mono-substituted aryl groups, phenyl or naphthyl, phenoxy, mono- or di-(C1-C3)alkyl substituted phenoxy, mono- or di-(C1-C3)alkoxy substituted phenoxy, mono(C1-C3)alkylamino, phenylamino, mono- or di-(C1-C3)alkyl substituted phenylamino, or mono- or di-(C1-C3)alkoxy substituted phenylamino, each of said aryl group substituents being C1-C3 alkyl or C1-C3 alkoxy.
Preferably, B and Bxe2x80x2 are each selected from the group consisting of: (a) the mono R-substituted phenyl; (b) phenyl, mono-substituted and di-substituted phenyl; (c) the unsubstituted, mono- and di-substituted heteroaromatic groups furanyl, benzofuran-2-yl, thienyl, benzothien-2-yl, dibenzofuran-2-yl, and dibenzothien-2-yl, each of said phenyl and heteroaromatic substituents in (b) and (c) being selected from the group consisting of hydroxy, aryl, arlyoxy, aryl(C1-C3)alkyl, amino, mono(C1-C3)alkylamino, di(C1-C3)alkylamino, N-(C1-C3)alkylpiperazino, indolino, piperidino, morpholino, pyrryl, C1-C3 alkyl, C1-C3 chloroalkyl, C1-C3 fluoroalkyl, C1-C3 alkoxy, mono(C1-C3)alkoxy(C1-C3)alkyl, chloro and fluoro; (d) the groups represented by graphic formulae VA and VB wherein L is carbon and M is oxygen, R14 is C1-C3 alkyl or C1-C3 alkoxy; R15 and R16 are each hydrogen or C1-C4 alkyl; and q is 0 or 1; (e) C1-C4 alkyl; and (f) the group represented by graphic formula VC, wherein P is hydrogen or methyl and Q is phenyl or mono-substituted phenyl, said phenyl substituent being C1-C3 alkyl, C1-C3 alkoxy or fluoro; or B and Bxe2x80x2 taken together form fluoren-9-ylidene, mono-substituted fluoren-9-ylidene or a member selected from the group consisting of saturated C3-C8 spiro-monocyclic hydrocarbon rings, saturated C7-C10 spiro-bicyclic hydrocarbon rings, and saturated C7-C10 spiro-tricyclic hydrocarbon rings, said fluoren-9-ylidene substituent being selected from the group consisting of C1-C3 alkyl, C1-C3 alkoxy, fluoro and chloro.
More preferably, the naphthopyran of the present invention is represented by graphic formula III, each R3 is the group R represented by formula IVE or IVF of each R3 is selected from the group consisting of hydrogen, C1-C3 alkyl, phenyl, mono- or di-substituted phenyl and the group xe2x80x94OR10, wherein R10 is C1-C3 alkyl and said phenyl substituents are methyl or methoxy. R5 and R6 are each the group R, hydrogen, hydroxy, C1-C4 alkyl or the group xe2x80x94OR11, wherein R11 is C1-C3 alkyl. B and Bxe2x80x2 are each selected from the group consisting of: (a) the mono-R-substituted phenyl; (b) phenyl, mono- and di-substituted phenyl, preferably substituted in the meta and/or para positions; (c) the unsubstituted, mono- and di-substituted heteroaromatic groups furanyl, benzofuran-2-yl, thienyl and benzothien-2-yl, each of said phenyl and heteroaromatic substituents in (b) and (c) being selected from the group consisting of hydroxy, C1-C3 alkyl, C1-C3 alkoxy, phenyl, indolino, fluoro and chloro; (d) the group represented by graphic formulae VA wherein L is carbon and M is oxygen, R14 is C1-C3 alkyl or C1-C3 alkoxy; R15 and R16 are each hydrogen or C1-C3 alkyl; and q is 0 or 1; or B and Bxe2x80x2 taken together form fluoren-9-ylidene, adamantylidene, bornylidene, norbornylidene, or bicyclo[3.3.1]nonan-9-ylidene.
Compounds represented by graphic formulae I, II and III may be prepared by the following steps. In Reaction A, an excess of polyethylene glycol represented by general formula VI (wherein x is the same as for group xe2x80x94A or xe2x80x94Exe2x80x94) or another polyalkylene glycol is reacted with toluenesulfonyl chloride represented by graphic formula VII in the presence of pyridine (PY) at xe2x88x925xc2x0 C. to produce the hydroxy(polyethoxy)-p-toluenesulfonate represented by graphic formula VIII. See Bradshaw, J. S., et al, xe2x80x9cSynthesis of Macrocyclic Acetals Containing Lipophilic Substituentsxe2x80x9d, Tetrahedron, Vol. 43, No. 19, pp 4271 to 4276, 1987. 
In Reaction B, the alkoxylated toluenesulfonate represented by graphic formula VIII is reacted with a naphthopyran represented by graphic formula IX in the presence of anhydrous potassium carbonate, acetone solvent and heat to form the hydroxy end-capped alkoxylated naphthopyran of graphic formula IXA. The hydroxy end-capped alkoxylated naphthopyran of graphic formula IXA is further reacted with bromoacetic acid in the presence of a suitable base such as triethylamine to produce the pyran of graphic formula IA in which the terminal hydroxy has been end-capped with a carboxy-containing functionality. Alternatively, halogenated alkoxylated alcohols may be used in place of the alkoxylated toluenesulfonate to alkylate the hydroxy functionality using the aforementioned reaction conditions. Alkylating reactions are further described in Organic Synthesis, Vol. 31, pages 90-93, John Wiley and Sons, New York, N.Y.
The compound represented by graphic formula IX may be prepared by coupling a substituted naphthol with a propargyl alcohol. This procedure is described in U.S. Pat. No. 5,458,814, column 5, line 10 to column 7, line 38. The propargyl alcohol may be prepared according to the methods disclosed in U.S. Pat. No. 5,645,767, column 5, line 8 to column 6, line 30.
A propargyl alcohol containing a 9-julolidinyl or other benzo-fused cyclic amino groups, e.g., indolyl and tetrahydroquinolinyl, may be prepared by the Friedel-Craft""s acylation of the material with benzoyl chloride using aluminum chloride as the catalyst. The resulting amino substituted benzophenone may be reacted with sodium acetylide in a solvent such as dimethylformamide to produce a propargyl alcohol containing a benzo-fused cyclic amino substituent. The propargyl alcohol may be used in the hereinafter described coupling reaction to produce a naphthopyran having such a B or Bxe2x80x2 substituent. 
In Reaction C, a substituted naphthoic acid represented by graphic formula X is reacted with a polyethylene glycol represented by general formula VI using concentrated sulfuric acid and heat to form the alkoxylated naphthol represented by graphic formula XIA,. Alternatively X is reacted under similar conditions with glycerol to produce XIB. In graphic formula X, R2 and R3 are as previously defined. The alkoxylated naphthols represented by graphic formula XIA and XIB are coupled with the propargyl alcohol represented by graphic formula XII to form the alkoxylated naphthopyrans represented by graphic formula IB and IXB. Naphthopyran IXB is reacted with thionyl chloride to convert the terminal hydroxy to a chloride group. This chloride is further reacted with pentaerythritol to give polyhydroxylated naphthol represented by formula IC. 
In Reaction D, the alkoxylated toluenesulfonate represented by graphic formula VIII is reacted with a hydroxy substituted benzophenone represented by graphic formula XIII to form the alkoxylated benzophenone represented by graphic formula XIV. The alkoxylated benzophenone is reacted with sodium acetylide in a suitable solvent, such as anhydrous tetrahydrofuran (THF), to form the corresponding propargyl alcohol represented by graphic formula XV. The propargyl alcohol (XV) is coupled with the substituted naphthol of graphic formula XVI to form the alkoxylated naphthopyran represented by graphic formula IXC. The terminal hydroxy group of the (poly)alkoxy grouping on naphthopyran IXC is metalated with sodium hydride, followed by reaction with succinic anhydride. Final acidification yields the carboxylated alkoxylated naphthopyran IIA. 
In Reaction E, glycerol is reacted with a hydroxy substituted acetophenone, benzophenone or benzaldehyde represented by graphic formula XVII in the presence of acid to form the corresponding polyhydroxylated acetophenone, benzophenone or benzaldehyde. The compound of graphic formula XVIII is reacted with an ester of succinic acid such as dimethyl succinate represented by graphic formula XIX. Addition of the reactants to a solvent, e.g., toluene, containing potassium t-butoxide or sodium hydride as the base, yields the Stobbe condensation half ester represented by graphic formula XX. The half ester (XX) undergoes cyclodehydration in the presence of acetic anhydride to form the alkoxylated acetoxynaphthalene represented by graphic formula XXI. This product is reacted with hydrochloric acid (HCl) and an anhydrous alcohol such as anhydrous methanol to form the corresponding naphthol represented by graphic formula XXII. The naphthol (XXII) is coupled with a propargyl alcohol represented by graphic formula XII to form the polyhydroxylated naphthopyran represented by graphic formula ID. 
In Reaction F, the polyhydroxylated benzophenone represented by graphic formula XIVA (prepared by reaction of pentaerythritol with (bis)bromomethylbenzophenone in the presence of sodium hydride) is reacted with an ester of succinic acid such as dimethyl succinate represented by graphic formula XIX. Addition of the reactants to a solvent, e.g., toluene, containing potassium t-butoxide or sodium hydride as the base, yields the Stobbe condensation half esters represented by graphic formula XXIII. The half ester undergoes cyclodehydration in the presence of acetic anhydride to form the alkoxylated acetoxynaphthalene represented by graphic formulae XXIV. This product is reacted with hydrochloric acid (H+) and an anhydrous alcohol such as anhydrous methanol to form the corresponding naphthol represented by graphic formula XXV. The naphthol is coupled with propargyl alcohol represented by graphic formula XII to form the polyhydroxylated naphthopyran represented by graphic formula IE. 
In Reaction G, the compound represented by graphic formula XXIX is reduced with lithium aluminum hydride (LAH) to produce the compound represented by graphic formula XXX. Procedures for preparing the compound of graphic formula XXIX are disclosed in the afore-referenced U.S. Pat. No. 5,645,767. An ethoxylated pentaerythritol containing 4 randomly distributed ethoxy equivalents per mole is reacted with the compound of graphic formula XXX using an acid (H+) to form several ethoxylated isomers including the polyhydroxylated indeno-fused naphthopyran of graphic formula IIIA. 
In reactions H and I, the indeno-fused naphthopyrans represented by graphic formula XXIX may be substituted with group R as the R3 substituent. For example, compound XXVII in Reaction F may be cyclized under acidic conditions and coupled with a propargyl alcohol to produce indeno-fused naphthopyrans having the R group at the 6 position. The same may be done to compound XXVIII to produce an indeno-fused naphthopyran having the R group at the 11 position.
In Reaction H, the indeno-fused naphthopyran represented by graphic formula XXIX is first reacted with compound XXXI and then cyclized under acidic conditions (H+) to produce the compound represented by graphic formula IIIB. Substituents R15 and R16 are the same as previously described. Compound XXXI may be prepared from the corresponding phenethyl bromide via reaction with magnesium in ethereal solvents. 
In Reaction I, the indeno-fused naphthopyran represented by graphic formula XXIX is first reacted with compound XXXII and then cyclized under acidic conditions (H+) to produce the compound represented by graphic formula IIIC. T in compound XXXII may be selected from the groups, (xe2x80x94Oxe2x80x94), (xe2x80x94CH2xe2x80x94), and (xe2x80x94CHxe2x95x90CHxe2x80x94) and m is an integer of from 0 to 2. When T is (xe2x80x94CH2xe2x80x94), m equals 1-2, when T is (xe2x80x94CHxe2x95x90CHxe2x80x94), m equals 1 and when m equals 0, T is a carbon-carbon bond. 
Reactions C, E, F, G, H and I produce naphthopyrans having a hydroxylated R group which may be used in reactions to form polyurethane polymers. The hydroxyl functional R group substituted naphthopyrans may also be reacted with methacryloyl chloride or methacrylic anhydride in the presence of an acid acceptor to produce a methacryloxy capped R group substituted naphthopyran or with epichlorohydrin in the presence of a base to produce an epoxy capped R group substituted naphthopyran. The hydroxylated R group may also be condensed with the appropriate sulfo- or sulfono-containing groups in the presence of acid to produce sulfo- or sulfono-capped R group substituted naphthopyrans.
The naphthopyran compounds represented by graphic formulae I, II and III may be used in those applications in which organic photochromic substances may be employed, such as optical lenses, e.g., vision correcting ophthalmic lenses, contact lenses and plano lenses, face shields, goggles, visors, camera lenses, windows, automotive windshields, aircraft and automotive transparencies, e.g., T-roofs, sidelights and backlights, plastic films and sheets, textiles and coatings, e.g., coating compositions. As used herein, coating compositions are defined herein to include polymeric coating compositions prepared from materials such as polyurethanes, epoxy resins, aminoplast resins, poly(meth)acrylate resins, polyanhydride resins and other resins used to produce synthetic polymers; paints, i.e., a pigmented liquid or paste used for the decoration, protection and/or the identification of a substrate; and inks, i.e., a pigmented liquid or paste used for writing and printing on substrates, which include paper, glass, ceramics, wood, masonry, textiles, metals and polymeric organic materials. Coating compositions may be used to produce polymeric coatings on optical elements, verification marks on security documents, e.g., documents such as banknotes, passport and drivers"" licenses, for which authentication or verification of authenticity may be desired.
Depending on the R group and number of such groups used as substituents, the photochromic compounds of the present invention may be soluble in water, water soluble polymers or water containing polymers. Soluble is defined as miscible to the extent of at least 1 gram per liter. The water solubility of some of the photochromic compounds of the present invention offers handling and processing advantages not achieved by water insoluble photochromic compounds. In particular, the use of hazardous organic solvents as carriers for photochromic compounds is avoided. Also avoided is the use of such solvents in cleaning excess photochromic material from the surface of polymeric substrates after an imbibition or transfer process.
The 2H-naphtho[1,2-b]pyrans represented by graphic formula I exhibit color changes from colorless to colors ranging from yellow to red/purple. The 3H-naphtho[2,1-b]pyrans represented by graphic formula II exhibit color changes from colorless to colors ranging from yellow to orange and red. The indeno[2,1-f]naphtho[1,2-b]pyrans represented by graphic formulae III exhibit color changes from colorless to colors ranging from orange to blue/gray.
Examples of contemplated naphthopyrans within the scope of the invention are the following:
(a) 3,3-di(4-methoxyphenyl)-6,11,13-trimethyl-13-(2,3-dihydroxy)propoxy-indeno[2,1-f]naphtho[1,2-b]pyran;
(b) 3,3-di(4-methoxyphenyl)-6,11,13-trimethyl-13-(2-(2,2-bis[(2-hydroxyethoxy)methyl]-3-hydroxypropyloxy)ethoxy)-indeno[2,1-f]naphtho[1,2-b]pyran;
(c) 3,3-di(4-methoxyphenyl)-6,11-dimethoxy-13-methyl-13-(2,3-dihydroxy)propoxy-indeno[2,1-f]naphtho[1,2-b]pyran;
(d) 3-phenyl-3-(4-morpholinophenyl)-13-methyl-13-(2,3-dihydroxy)propoxy-indeno[2,1-f]naphtho[1,2-b]pyran;
(e) 2,2-diphenyl-5-((2,3-dihydroxy)propoxy)-carbonyl-8-methyl-[2H]-naphtho[1,2-b]pyran;
(f) 3,3-di(4-methoxyphenyl)-6,11,13-trimethyl-13-(2-(3-carboxypropanoyloxy)ethoxy)-indeno[2,1-f]naphtho[1,2-b]pyran;
(g) 3,3-di(4-methoxyphenyl)-6,11-dimethoxy-13-methyl-13-(2,3-dimethacryloxy)propoxyindeno[2,1-f]naphtho[1,2-b]pyran;
(h) 3,3-di(4-methoxyphenyl)-6,11,13-trimethyl-13-(2,3-di(2-sulfonoethyloxy))propoxy-indeno[2,1-f]naphtho[1,2-b]pyran;
(i) 3-phenyl-3-(4-morpholinophenyl)-6,11-dimethoxy-13-methyl-13-(2,3-di(4-sulfonophenoxy))propoxy-indeno[2,1-f]naphtho[1,2-b]pyran; and
(j) 3,3-di(4-methoxyphenyl)-6,11-dimethoxy-13-methyl-13-(2,3-di(epoxymethoxy))propoxy-indeno[2,1-f]naphtha[1,2-b]pyran.
It is contemplated that the photochromic naphthopyrans of the present invention may each be used alone, in combination with other naphthopyrans of the present invention, or in combination with one or more other appropriate complementary organic photochromic materials, i.e., organic photochromic compounds having at least one activated absorption maxima within the range of between about 400 and 700 nanometers (or substances containing the same) and which color when activated to an appropriate hue.
The complementary organic photochromic materials may include other polymerizable photochromic compounds, such as those disclosed in U.S. Pat. Nos. 4,719,296; 5,166,345; 5,236,958; 5,252,742; 5,359,085; and 5,488,119. Further examples of complementary organic photochromic compounds include other naphthopyrans and indenonaphthopyrans, chromenes and oxazines, substituted 2H-phenanthro[4,3-b]pyran and 3H-phenanthro[1,2-b]pyran compounds, benzopyran compounds having substituents at the 2-position of the pyran ring and mixtures of such photochromic compounds. Such photochromic compounds are described in U.S. Pat. Nos. 3,562,172; 3,567,605; 3,578,602; 4,215,010; 4,342,668; 4,816,584; 4,818,096; 4,826,977; 4,880,667; 4,931,219; 5,066,818; 5,238,981; 5,274,132; 5,384,077; 5,405,958; 5,429,774; 5,458,814, 5,466,398; 5,514,817; 5,552,090; 5,552,091; 5,565,147; 5,573,712; 5,578,252; 5,637,262; 5,645,767; 5,656,206; 5,658,500; 5,658,501; 5,674,432, 5,698,141, 5,723,072, 5,744,090, 5,783,116, 5,808,063, 5,811,034, 5,869,658, 5,879,592, 5,891,368 and 5,961,892. Spiro(indoline)pyrans are also described in the text, Techniques in Chemistry, Volume III, xe2x80x9cPhotochromismxe2x80x9d, Chapter 3, Glenn H. Brown, Editor, John Wiley and Sons, Inc., New York, 1971.
Other complementary photochromic substances contemplated are metal-dithiozonates, e.g., mercury dithizonates, which are described in, for example, U.S. Pat. No. 3,361,706; and fulgides and fulgimides, e.g., the 3-furyl and 3-thienyl fulgides and fulgimides, which are described in U.S. Pat. No. 4,931,220 at column 20, line 5 through column 21, line 38.
The photochromic articles of the present invention may contain one photochromic compound or a mixture of photochromic compounds, as desired.
The photochromic compounds of the present invention may be associated with a polymeric organic host material or other substrate by various means. They may be incorporated, i.e., dissolved and/or dispersed, into the host material, polymerized with other components of the host material, and/or incorporated into a coating applied to a substrate, e.g., a polymeric coating applied to one surface of the polymeric organic host material.
Each of the photochromic substances described herein may be used in amounts (or in a ratio) such that an organic host material or substrate to which the photochromic compounds or mixture of compounds is associated, exhibits a desired resultant color, e.g., a substantially neutral color when activated with unfiltered sunlight, i.e., as near a neutral color as possible given the colors of the activated photochromic compounds. Neutral gray and neutral brown colors are preferred. Further discussion of neutral colors and ways to describe colors may be found in U.S. Pat. No. 5,645,767 column 12, line 66 to column 13, line 19.
The amount of the photochromic naphthopyrans to be applied to or incorporated into a coating composition or host material is not critical provided that a sufficient amount is used to produce a photochromic effect discernible to the naked eye upon activation. Generally such amount can be described as a photochromic amount. The particular amount used depends often upon the intensity of color desired upon irradiation thereof and upon the method used to incorporate or apply the photochromic compounds. Typically, the more photochromic compound applied or incorporated, the greater is the color intensity up to a certain limit.
The relative amounts of the aforesaid photochromic compounds used will vary and depend in part upon the relative intensities of the color of the activated species of such compounds, the ultimate color desired and the method of application to the host material or substrate. Generally, the amount of total photochromic compound incorporated into or applied to a photochromic optical host material may range from about 0.05 to about 2.0, e.g., from 0.1 to about 1.0, milligrams per square centimeter of surface to which the photochromic compound is incorporated or applied. The amount of photochromic material incorporated into a coating composition may range from 0.1 to 40 weight percent based on the weight of the liquid coating composition.
The photochromic naphthopyrans of the present invention may be associated with the host material by various methods described in the art. See, for example, column 13, lines 40 to 58 of U.S. Pat. No. 5,645,767. Aqueous or organic solutions of the photochromic compounds may be used to incorporate the photochromic compounds into a polymeric organic host material or other materials such as textiles and polymeric coating compositions. Polymeric coating compositions may be applied to the substrate using a coating process such as that described in U.S. Pat. No. 3,971,872.
Application of the polymeric coating may be by any of the methods used in coating technology such as, for example, spray coating, spin coating, spread coating, curtain coating, dip coating, casting or roll-coating and methods used in preparing overlays, such as the method of the type described in U.S. Pat. No. 4,873,029. The application method selected also depends on the thickness of the cured coating. Coatings having a thickness ranging from 1 to 50 microns may be applied by conventional methods used in coating technology. Coatings of a thickness greater than 50 microns may require molding methods typically used for overlays.
The host material will usually be transparent, but may be translucent or even opaque. The host material need only be pervious to that portion of the electromagnetic spectrum, which activates the photochromic substance, i.e., that wavelength of ultraviolet (UV) light that produces the open or colored form of the substance and that portion of the visible spectrum that includes the absorption maximum wavelength of the substance in its UV activated form, i.e., the open form. Preferably, the host color should not be such that it masks the color of the activated form of the photochromic compounds, i.e., so the change in color is readily apparent to the observer. Compatible tints may be applied to the host material as described in U.S. Pat. No. 5,645,767 in column 13, line 59 to column 14, line 3.
Most preferably, the polymeric organic host material is a solid transparent or optically clear material, e.g., materials suitable for optical applications, such as plano, ophthalmic and contact lenses, windows, automotive transparencies, e.g., windshields, aircraft transparencies, plastic sheeting, polymeric films, etc.
Examples of polymeric organic host materials which may be used with the photochromic compounds described herein include: polymers, i.e., homopolymers and copolymers, of the bis(allyl carbonate)monomers, diethylene glycol dimethacrylate monomers, diisopropenyl benzene monomers, ethoxylated bisphenol A dimethacrylate monomers, ethylene glycol bismethacrylate monomers, poly(ethylene glycol)bismethacrylate monomers, ethoxylated phenol bismethacrylate monomers, alkoxylated polyhydric alcohol acrylate monomers, such as ethoxylated trimethylol propane triacrylate monomers, urethane acrylate monomers, such as those described in U.S. Pat. No. 5,373,033, and vinylbenzene monomers, such as those described in U.S. Pat. No. 5,475,074 and styrene; polymers, i.e., homopolymers and copolymers, of mono-functional acrylate and/or methacrylate monomers, polyfunctional, e.g., di- or multi-functional, acrylate and/or methacrylate monomers, poly(C1-C12 alkyl methacrylates), such as poly(methyl methacrylate), poly(oxyalkylene)dimethacrylate, poly(alkoxylated phenol methacrylates), cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl chloride), poly(vinylidene chloride), poly(vinylpyrrolidone), poly((meth)acrylamide), poly(dimethylacrylamide), poly(hydroxyethyl methacrylate) poly((meth)acrylic acid), polyurethanes, polythiourethanes, thermoplastic polycarbonates, polyesters, poly(ethylene terephthalate), polystyrene, poly(alpha methylstyrene), copoly(styrene-methyl methacrylate), copoly(styrene-acrylonitrile), polyvinylbutyral and polymers, i.e., homopolymers and copolymers, of diallylidene pentaerythritol, particularly copolymers with polyol (allyl carbonate) monomers, e.g., diethylene glycol bis(allyl carbonate), and acrylate monomers, e.g., ethyl acrylate, butyl acrylate. Further examples of polymeric organic host materials are disclosed in the U.S. Pat. No. 5,753,146, column 8, line 62 to column 10, line 34.
Transparent copolymers and blends of transparent polymers are also suitable as host materials. Preferably, the host material or substrate for the photochromic polymeric coating composition is an optically clear polymerized organic material prepared from a thermoplastic polycarbonate resin, such as the carbonate-linked resin derived from bisphenol A and phosgene, which is sold under the trademark, LEXAN; a polyester, such as the material sold under the trademark, MYLAR; a poly(methyl methacrylate), such as the material sold under the trademark, PLEXIGLAS; polymerizates of a polyol(allyl carbonate)monomer, especially diethylene glycol bis(allyl carbonate), which monomer is sold under the trademark CR-39, and polymerizates of copolymers of a polyol(allyl carbonate), e.g., diethylene glycol bis(allyl carbonate), with other copolymerizable monomeric materials, such as copolymers with vinyl acetate, e.g., copolymers of from 80-90 percent diethylene glycol bis(allyl carbonate) and 10-20 percent vinyl acetate, particularly 80-85 percent of the bis(allyl carbonate) and 15-20 percent vinyl acetate, and copolymers with a polyurethane having terminal diacrylate functionality, as described in U.S. Pat. Nos. 4,360,653 and 4,994,208; and copolymers with aliphatic urethanes, the terminal portion of which contain allyl or acrylyl functional groups, as described in U.S. Pat. No. 5,200,483; poly(vinyl acetate), polyvinylbutyral, polyurethane, polythiourethanes, polymers of members of the group consisting of diethylene glycol dimethacrylate monomers, diisopropenyl benzene monomers, ethoxylated bisphenol A dimethacrylate monomers, ethylene glycol bismethacrylate monomers, poly(ethylene glycol) bismethacrylate monomers, ethoxylated phenol bismethacrylate monomers and ethoxylated trimethylol propane triacrylate monomers; cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, polystyrene and copolymers of styrene with methyl methacrylate, vinyl acetate and acrylonitrile.
More particularly contemplated is use of the photochromic naphthopyrans of the present invention with optical organic resin monomers used to produce optically clear coatings and polymerizates, i.e., materials suitable for optical applications, such as lenses for use in a pair of spectacles, e.g., plano or ophthalmic spectacle lenses, or for use as contact lenses. Optically clear polymerizates may have a refractive index that may range from about 1.35 to about 1.75, e.g., from about 1.495 to about 1.66.
Specifically contemplated are polymerizates of optical resins sold by PPG Industries, Inc. under the CR-designation, e.g., CR-307 and CR-407, and polymerizates prepared for use as hard or soft contact lenses. Methods for producing both types of contact lenses are disclosed in U.S. Pat. No. 5,166,345, column 11, line 52, to column 12, line 52.
Additional polymerizates contemplated for use with the photochromic naphthopyrans of the present invention are polymerizates used to form soft contact lenses with high moisture content described in U.S. Pat. No. 5,965,630 and extended wear contact lenses described in U.S. Pat. No. 5,965,631.